SU749081A1 - Method for antistatic treatment of thermoplastic polymers - Google Patents

Abstract

METHOD OF ANTISTATIC TREATMENT OF THERMOPLASTIC POLYMERS by applying to the surface or; the introduction of piperidini into the mass of salts, on tl and h ay i and so. that, in order to improve the antistatic properties at low relative humidity

Description

The invention relates to a method for the antistatic treatment of thermoplastic polymers by applying them or incorporating pyridine into the mass. The method of antistatic treatment of polymers by applying them or introducing into their mass of salts of nitrogen-containing heterocycle salts of morpholini that do not contain fluorine, for example, naphthenyl ethylmorphol liylacetate, is known. According to this method, the specific surface electrical resistance (ps) at a relative humidity of 65jb5% and a temperature of 20+ is 5.7–10–3 ohms (when applied on the surface and 1.110–1.910 ohms (when introduced into the mass). At low (20-40%) relative air humidity, which is characteristic of closed rooms in the heat during the period, the antistatic properties deteriorate. The closest to the technical essence and the achieved effect to the proposed invention is the method described in source 2. According to it, the decrease in electrificationpolymers are carried out by applying to them or adding to the mass of nitrogen-containing heterocycles-bis-salts of piperidinium that do not contain fluorine (for example, dioctyl chloride-1,4-di-H-piperidylbutane, etc.). p5 polymers with a relative humidity of 65 ± 5% and a temperature of 20+ 3 ° C is 6.0-10 - 2.5-108 ohm (when applied on the surface) and 4.1-10-1 ohm (when administered internally). However, the antistatic properties of polymers with relative 20-40% moisture is deteriorated to 7.0-10 8, 3; iO The aim of the invention is to improve the reduction of antistatic reduction by electrifying Polymers with a relative humidity of 20–40%. This is achieved by using fluorine containing piperidinium salts of the general formula as piperidinium salts in the method of reducing the electrification of thermoplastic polymers. RI BjJ where R is hydrogen or C -C-alkyl, R is CHjCH OH (only in the case of fluorine-containing anion), fluorine-containing groups of the formulas (; H2H20 (3 {С2) (where n 0-11), g m CH2 (JH20C- / FV, CHgCHgOCCFg- ou / fu CH2CH20 $ 02-f -OC9Fi7, AS (Jr, Brr.lTOjj ClO, CH3 $ 04, (CH312Rl, CHjtioo-, CHjCeHi Os (only in the case of fluorine-containing groups in the cation, O-SRgSOO Os OCO (CF2) CF5, (where m 0-11). When surface coating of 0.24, 0% solutions of fluorine-containing piperidinium salts on polymers, the specific surface resistance of the samples is 3.7109 -3.8 ohms and TjOlO ® - 1.0-10 Ohm at 20t3c and, accordingly, at a relative humidity of air a 20 and 40%. Samples of polyethylene with the internal introduction of 0.5-4.0 wt.% fluorine-containing salts of piperidini according to the proposed method have p 4, 210. Ohms and 1.6. - 7.0-10 00m at 20+ 3 ° C. And, respectively, at a relative humidity of 20 and 40%, the yield strength at stretching (Gt) is 87-220 kgf / cm, breaking stress at stretching (br) 105-130 kgf / cm and elongation at break () 266-600%. Polymer samples obtained by the proposed method. Have increased water resistance of the antistatic coating and have better antistatic properties compared with the prototype (reference examples 22-29 and 34-36) and with samples of polymers treated with widely used industrial type Alcamone pQ g 3.3 KG Ohm with an internal introduction to it). The antistatic agents according to the invention are applied to the surface of polymers from solutions with a concentration of 0.4.0% by weight, or introduced into the mass of polymers in an amount of 0.5-4.0% by weight. Target additives such as dyes, stabilizers, plasticizers, etc. can be used at the same time. Antistatics Can be introduced into the polymer melt by conventional methods on rollers, in a heavy type plastic mixer or in an extruder.

Example 1. Disks with a diameter of 50 mm and toli; another 1 mm from low density polyethylene (LDPE is immersed for 20 s in a 0.2% solution of perfluorotetrahydrofuryl-C-difluoroacetate hydroxyethylpiperidini in ethyl alcohol and then dried at room temperature in the vertical position For 2 hours, the samples treated in this way are 3.8-10 Ohms and 1.3-10 Ohms at 20 + 3 ° C and, respectively, relative humidity 20i5 and 40 ± 5%.

Example 2. Disks with a diameter of 50 mm and a thickness of 1 mn made of polypropylene (PP) are immersed for 20 s in a 0.2% solution of perfluorotetrahydrofuryl-d-difluoroacetate 1- / 3-hydroxyethylpiperidini in ethyl alcohol and then dried at room temperature in the vertical For 2 hours, the PS of samples treated in this way is 2.910 O and I.OIO Ohms at 20 ± 3 ° C, respectively, relative humidity and 40 + 5%.

Example 3. Disks 50 mm in diameter from block polystyrene (PSB) are immersed for 20 s in a 0.2% solution of perfluorotetrahydrofuryl-L-: difluoroacetate 1 -oxyethylpiperidini in ethyl alcohol and then dried at room temperature in the vertical position in for 2 hours The PS of samples treated in this way is 3, 8-10 ohms and 1.210 ohms, with and respectively a relative humidity of 20 ± 5% and 40 ± 5% ... .

Example 4. Disks with a diameter of 50 mm and polymethyl methacrylate (.PMMA) are immersed for 20 s in a 0.2% solution of perfluorotetrahydrofuryl-D-difluoroacetate 1-B-hydroxyethylpiperidini in ethyl alcohol and then dried at room temperature in a vertical position for 2 hours . The PS of samples treated in this way is 1.010 ohms and 6.3 "10 ohms at 20 + 3 ° C (AND respectively, relative humidity 20 ± .5% and 40 + 5%.

) 2 PRI me R s 5-21. EXPERIENCE was carried out under the conditions of Example 1, but different polymers and fluorinated antistatics were used and their quantities varied. The data are given in the table. ,

. Examples 22-29 (coMtr). The experience is conducted under conditions. Example 1, but using different polymers and other antistatic agents and vary their amounts.

The data obtained are given in. the table.

Example 30. Low density polyethylene is mixed with 1 wt.%

perfluorotetrahydrofuryl-oC-difluoroacetate-1- | 1-hydroxyethylpiperidinium on rollers at a temperature of 135 + 5 ° С for 7 minutes. The samples obtained have a PS of 1.2-10 ohms and 6.0. at. and, respectively, the relative humidity of 20 + 5% and 40 + 5% and have BT 101 kgf / cm, br 155 kgf / s and 590%.

Example 31. Low density polyethylenes are mixed with 4 wt.% I of 1-B-hydroxyethylpiperidini perfluorovalerate on rollers at a temperature of 135+. within 7 min. The samples obtained have ps b, and 2.010 ° ohms at 20 + 3 ° С and, respectively, relative humidity of 20 + 5% and 40 + 5%, and have bt 94 kgf / cm, dp 105 kgf / cm and 500%.

EXAMPLE 32. Low density polyethylene is mixed with 0.6 wt.% Of nitrate H-butyl-K-p- (perfluorlauryl. Oxy ethyl piperidinium on a roll at a temperature of 135 + 5 ° C for 7 minutes The obtained samples have PS GD-Yu Ohms and 7, Ohms at 20 + 3®С and, respectively, relative humidity 20 + 5% and 40 ± 5% and have bg 3 kgf / cm, jp 111 kgf / cm2 and E 600% .L

Example 33. High-density polyethylene is mixed with 4.0 wt.% Dimetaphosphate and -Etil-H-L- (perfluorovaleryloxy) ethyl piperidinium on rollers at a temperature of 155 + 5 C for 7 minutes. The obtained samples have a PS of 4.310 Ohms and 1.6 - 10 Ohms at and, respectively, relative humidity 20 + 5% and 40 + 5% and have d g 220 kgf / cm br 130 kgf / cm and B 266%.

Example 34 (control). Low-density polyethylene is mixed with 0.5 wt.% Dioctadecyl bromide-1, 4-di-H-piperididicythylamine on a roller at a temperature of 135 + 5 s for 7 minutes. The samples obtained have a Pg of 6.1-10 ohms and 9, at 20 + 3 ° С and, respectively, relative humidity of 20 + 5%. and 40. + 5% and have Bt 7 kgf / cm, 135 kgf / cm 2 and 600%.

EXAMPLE 35 (control) Low-density polyethylene is mixed with 4.0% by weight dioctadecylbromide-1, 4-di-H-piperidyldiethylamine on a roll at temperature C for 7 minutes. The obtained samples possess PS 1.0–10 Ohms and 9.1–10 Ohms at 20 + 3С and respectively relative humidity 20 + 5% and 40 + 5% and have From 85 kgf / cm, dp 124 kgf / cm and e 540 %

Example 36 (control), High-density polyethylene is mixed with 4.0 wt.% Dioctadecyl peroxide (Chlorate-1,4-di-H-piperidylbutan on. Eltz at a temperature of 155 + .5 ° C

p for 7 minutes The obtained samples possess Pg 9.0- and 1.0 Ohm at 20 + 3, and respectively relative humidity 20 + 5 and 40 + 5% and have 6 g 240 kgf / cm, br 136 kgf / cm and e: 325%.

The present invention improves the antistatic properties of thermoplastic polymers at low relative humidity. Predpagaeml method can be used to reduce the electrified plastic parts of measuring instruments, radio equipment, optical parts, etc., operated in closed

5 rooms in conditions of low relative humidity. This will increase the accuracy of measurements and the reliability of devices as a result of eliminating the influence of static electricity charges.

PMMA

Perfluorotetrahydrofluoryl-of-difluoroacetate 1 (-oxyethylpiperidini 4, 0

Perfloraverat 1PEN

-p-hydroxyethylpiperidini 1, 0

PMMA

Bromide N-ethyl-H-1rt - (perfluorovaleryloxy) ethyl / piperidini 2, 0

sing

Bromide K-ethyl-H- (p-perfluorotetrahydrofuryl-y-difluoroacetoxyethyl) piperidini 3, 0

LDPE

Bromide N-ethyl-H (. {-Perfluorohexahydrobenzoethyl) piperidini 2, 0

0 11 12

pp

Same2.0

PMMA LDPE

N-I- (p-perfluorononenyloxyferylsulfonyl) hydrochloride, hydroxyethylpiperidine 2.0

3 14 15

N-butyl-Kg Nitrate

PMMA

tip- (perfluorlaurilloxy) ethyl piperidi

Nor 1.0 LDPE

Perchlorate H-ethyl-K- p- (perfluoroacetyloxy) ethyl piperidin i3.0 PSB

Metasulfate N-ethyl-N-p - (perfluorovaleryloxy) ethyl piperidium 2, 0

1,010

one,

1,710

2.7-10

3.4-10

4.610

M

40

0.5

1.0-10

5.0-10

ten

.1П

2.5-10

1.3 “10

7.0-10 2.4-109

5.0-10 8.710

1.610

9.0-10

Table continuation

Claims (1)

METHOD FOR ANTISTATIC TREATMENT OF THERMOPLASTIC POLYMERS by, coating or introducing into the mass of piperidinium salts, from. In addition, in order to improve the antistatic properties at low relative humidity (20-40%), fluorine-containing piperidinium salts of the general formula are used as piperidinium salts: - hydrogen, SS ₄ -alkyl, - CH ^ CHjOH (Only in the case of a fluorine-containing anion), fluorine-containing groups of form ₂ sn ₂ oc (<* F ₂ ) _n cf ₅ / о i 0-11 _t where _ n _r Ί <ίΗ ₂ (ίΗ ₂ οΰ- ^ τ ^, <jh ₂ ch ₂ occf-QP - of about ₂ or CH <JH ₂ OSO _t - ^ y OC ₉ F ₁₇ · A = (1G, Br, K0 ₅ S10f, CH J & O4 (SN.3) ₂ U04 ₅ 1 CH C (S, e _"5 $ H 0z, CH _e C _b H _{June 4} (^ (only in the case of fluorine-containing groups in the cation) Lg J-CF ₂ C00 ^_ "ly (where a = 0-11). '' SU. ”749081